Composition of matter



Patented Apr. 1,1941

COIHPOSITION OF MATTER.

Frank J. Calm and Benjamin E. Harris, Chicago,

Ill., assignors to The Emulsol Corporation, Chicago, 111., a corporationof Illinois io Drawing. Application April 13, 1939,

Serial No. 267,717

23 Claims.

This invention relates to the preparation of materials which aredispersible or emulsifiable in aqueous media as well as to thepreparation of dispersions or emulsions of oleaginous or similarmaterials in aqueous media and is particularly concerned with essential'oil preparations, fatsoluble vitamin preparations, and other food andmedicinal preparations such as those containing corpus luteum and thelike,'which are administered orally, subcutaneously, intravenously,intramuscularly o'r intraperitoneally.

Essential oils sch as lemon oil, orange oil and the like are used in thearts in the preparation of divers kinds of products such as candies andconfections, beverages, cosmetic creams, hair shampoos, and in variousother edible preparations as well as cosmetic and medicinalcompositions. In general, the proportion of essential oil in theultimate preparation in which it is employed is quite small, usuallybeing of the order of less than 1%. Since the essential oils areimmiscible with water, it has been customary to nocuousness to the humansystem of the glycols utilize them in conjunction with gums such-asquently a desideratum. Again, reference may be terioration or spoilagein storage and/or shipment.

In the art dealing with the administration of fat-soluble vitamins,notably vitamins A and D, important problems have arisen which, up tothe present time, have not been fully satisfactorily solved. In theirusual form, vitamin A and D preparations are of oleaginous character andtheir general distastefulness has introduced problems, particularly inconnection with oral adminwhich are employed as solvent media. for thevitamins A and D, there are certain very definite limitations upon thedegree to which such vitamin-solutions can be dispersed or distributedin water or other aqueous media. Beyond a certain point, depending uponthe particular gly'col employed, the further dilution with aqueousmaterials causes a flocculation or cloudiness with a concurrent loss ofthe desired uniformity and homogeneity which make for proper dosagerequirements.

The same or analogous problems arise in connection with the preparationof icings and candies including fudges, tofiees and the like whereproper distribution of oleaglnous materialsis fremade to gelatin dessertpowders, to prepared flour compositions, to the manufacture of sausagesand meat pastes which contain a signiflcant content of moisture, to thepreparation istration thereof to infants .and children. Nui merousattempts have been made to overcome these known objections byincorporating such vitamin concentrates into brea'd, ice cream, candy.margarine, buttencheese, peanut butter, salad dressings, cereals,andother food products.

Following this same general approach, it has been proposed toincorporate vitamin. A and D concentrates into aqueous materials such.as water, 'milk, soupssirups, fruit juices and the water-insoluble, much.difllcultyhas been ,en-

'countered in effecting a uniform distribution thereof in aqueous mediaand maintaining the necessary homogeneity in order to assure properdosage.- Various means have been utilized in an effort to cope with thisproblem and it has of soya bean milk, to the preparation of milkenriched with coconut oil or other oils and fats, and to the dispersionof oil-soluble colors or dyes in aqueous media. Similar problems arisein connection with the dispersion of vitamins on solid surfaces such ascereals and breakfast foods where a very small amount of activeingredient,

which is difllcultly soluble or insoluble in aqueous media, is desiredto be dispersed on large surfaces. In all of these and other cases,where a problem of dispersing or emulsifying a solid or a liquid isconcerned, particularly where the ma- I like. Since these vitamins arefat-soluble and improvemens brought about by the teachings herein areparticularly applicable to the fields of human foods and medicines aswell as foods and medicines for domesticated or other animals and thelike including, for example, dog foods, poultry feed, fish food, cattlefeed, and the like.

In accordance with the present invention, many of the difiicultiesheretofore encountered in the preparationof. products of the characterpremins or fat-soluble vitamins, particularly in the o C on form ofconcentrates thereof as well as irradiated ergosterol and solutionsthereof, brings (4) CnHz:-CO n -on-coon about entirely unexpectedresults.

Many of the chemical compounds disclosed 5 JI herein also enable. theprovitamin and fat-soluble vitamin preparations to'be dispersed or dis-Ha O H tributed into aqueous material to provide a fine. C0011 uniform,homogeneous suspension or colloidal dis- 0 persion which may be dilutedwith water or other aqueous materials without disturbing the stabilu u--0-CHz-(CHOHh-CH-C00H ity or homogeneity of the product. Many of theemcee];

compounds disclosed herein, such as, for example, the reaction productof mono-olein with the di-acetic acid ester of tartaric acid anhydride,do not curdle but retain their desired (a (a properties even whenextensively diluted with water or aqueous material after initialdispersion. (6) c'mwc 0 0 0 o C C'HrcH c on In general, the compoundsand reaction products which are employed for the purposes of and inaccordance with the present invention are most suitably prepared byreacting a lower mo- Y H lecular weight carboxylic acid ester of an an-(7) C1H" .O' .CH,

hydride of an hydroxypolycarboxylic acid with an alcohol containing atleast four carbon atoms 5 H(|} O- (PC0011 and preferably from eight toeighteen carbon H2C-"0( lJ-CH 0H000rr atoms. By way of illustration,this may be exo (Lo-0H1 o-c-cn. emplifiedby reacting the acetic acidester of I II citric acid anhydride with lauryl alcohol. 7

While many of the reaction products utilized p in accordance with thepresent invention may (3 H 0-13-01! best be defined in the form ofreaction products, they and particularly some of the more potent (8)cngwamcn-(cnomril 0 032-1: cHrcooH constituents thereof can, at least inpart, be char- 0011 It I acterized or described by way of structurali'or- 35 o o o o-o-om u (9) 0nH=r- :o-cmcn,-0-ccmc 'om%-ocmcm-o-c-onnnoon' o mulae. Illustrative examples of such compounds whose use hereinfalls within the scope of the on. o 0-mc1 invention are as mum's: (10)c1nud-o-oH, :K-on-cn-ooon -o-'-on=oi i ll u i 1 Ci7H35-COCH2(CHOH)4CHr-0-CCH-CH-C-OH l g 11) c11Hnco-cH:-0H-$-on o 5(|%-CHBr-CHCOH O 0 -o-crr= (2 nic-o-pazn o 0-0-03- 0 con on o H -oo-onr-oomooon 12 o1Ha- -o-c,nl-o-mm-o-e-n-oHro- -c-o4 3-05. 0= 0H 6ofro-c o-o cH; H: --OCaHi1 Q o o t I (3) H:C-o 'ciiH23 O 6 o 0 o o c d vo t H H 1a cmrL-o-oHP -wm-oi J-cn-c bc00B H, ocm -c-cni' 11% o o-ta-on,0-45-03, nc-o- -cn n- -on (14) cmJz-o-on--o-cm-on-om-o-c z cunu E1 Icm-c-on stanltial amount of a compound of the probable formula may bevaried and that supplementary processes of purification and the like mybe resorted to wherever found desirable or convenient. These and othervariations and modifications will be evident to those skilled in the artin the light of the guiding principles which are disclosed herein.

Example A 3.72 parts h e-weight of commercial lauaryl alcohol and 4.32parts by weight of the acetic acid ester of citnic acid anhydride wereheated to 100 Example 8 12.65 parts by weight of (ii-acetic acid ester dof tartaric acid anhydride and 10.6 parts by weight ofcommerciailaurylalcohol were heated to degreesC. with stirring. Aiterseveral minutes at temperature, the ail-hydride went into solution. Theresulting reaction product contained at least a substantial amount of acom pound of the probable formula 'ihe product is a substantiallyodorless transparent syrup with a faintly-hitter taste. On

heating at degrees C. for 1 hour, the bitter taste was eliminated.

Example 0 10.05 parts by weight of di-acetic acid ester of tartaric acidanhydride and 12.5 parts by weight of monolaurln (containing 042% freefatty acid) were heated at 100 degrees C. with stiming about 10 minutesbeing required for a homogeneous solution to form. The resultingproduct,

having at least'a substantial amount of a compound of theprobableformula was a transparent syrup the viscosity of which increased onprolonged heating. 7 V

In place of (ii-acetic acid ester of tartaric acid anhydnide, the aceticacid ester of citric acid anhydride may be employed. Furthermore,instead of monolaurin, the mcnolauric acid ester of diethyiene glycolmay be used. These and other substitutions are disclosed in detailhereinafter and apply to the present example as well as the otherexamples.

. Example 12 25.55 parts by weight of a product comprising mainly themonolauric acid ester of diglycerol degrees C. wirthst'irring untilpractically all of said anhydride went mu: solution. The resultwerereacted at degrees C. with stirring for several minutes with 16.0 partsby weight of distilled di acetic acid ester of tartaric acid anhydri-de.The resulting reaction product comprised a substance with the followingprobable ing reaction product contained at least a sub- 70 formula:

cure-0 11-0001;

' The above reaction was also carried out with equal parts by weight ofmonocaprylin and diacetic acid ester of tartaric acid anhydride. A

7.85 parts by weight of ethylene glycol monolauralte and 7.0 parts byweight of dl-acetic acid ester of tartaric acid anhydride were heated at150 degrees C. with stirring for approximately 5 minutes. The resultingreaction product was then neutralized with dilurte caustic sodasolution. lit contained at least a substantial amount of a compoundhaving the probable following formula:

Example G 5.65 parts by weight of normal octyl alcohol and 9.5 parts byweight d-i-acetic acid ester of tartaric acid anhydride were heated at150 degrees C. with stirring for approximately 5 minutes and then thereaction product was neutralized with caustic soda. The reaction productcontained a substantial amount of a product having the followingprobable formula: CHa--C0CH( O-CsHn CHs-(fi-O- H-COONa Example H v 13.45parts by weight of castor oil and 9.2 parts by weight of di-acetic acidester of tartaric acid anhydride were heated at 160 degrees C. withstir-ring for several minutes. The product was then neutralized withcaustic soda. It was watersoluble.

Example I 6.65 parts by weight of monostearin and 8.0 parts by weight ofdi-acetic acid ester of tartaric acid anhydride were heated at 160degrees C.

with stirring for several minutes.

Example J 319 parts by weight of di-olein and parts by weight ofdi-acetic acid ester of tartaric acid anhydride where heated at 1'70degrees C. with agitation bymeans of a stream of carbon dioxide gas for10 minutes.

Example K 237 parts by weight of a product, consisting substantially ofmono-olein and 144 parts by weight of di-acetic acid ester of tartaricacid anhydride were heated slowly up to degrees C.

while passing a stream of carbon dioxide gas therethrough and thereaction mass was kept at such temperature for about 5 minutes. Thereaction product was a pale yellow viscous syrup.

Example L 389 parts by weight of the mono-'cetyl ether of diglycerol and216 parts by weight of di-acetic acid ester of tartaric acid anhydridewere heated with stirring at degrees C. for 10 minutes.

Instead of reacting the anhydride of acetic acid esters of citric andtartaric acids and the like with alcohols, it is also possible to reactsaid anhydrides with amines and amides such as hexyl amine, octyl amine,lauryl amine, stearyl amine, lauramide, stearamide, and the like toproduce new and useful products for the purposes of the presentinvention. An example of such procedure comprises heating 7.8 parts byweight of commercial n-1 laurylamine with 10 parts by weight ofdistilled di-acetic acid ester of tartaric acid anhydride at 140 degreesC. for several minutes. The resulting reaction product, a. brown syrup,when neutralized to phenolphthalein with caustic soda comprises il llCHs--COGHCNH CH2(ClIz)m-Cl1 a CHz-(fi-O- H-COONo The reaction productsof the present invention may be reacted with various alcohols such asbutyl alcohol, octyl alcohol, lauryl alcohol, cetyl alcohol, oleylalcohol, stearyl alcohol, as well as derivatives of polyhydroxysubstances such as monostearin, monolaurin, mono-olein, di-laurln,di-olein, mono-cetyl ether of glycerol, diethylene glycol mono-oleate,diethylene glycol monolaurate, and other alcohols such as thosedescribed hereinafter to produce reaction products having valuableproperties for the present purposes. The reaction in such cases appearsto be one of esterification between free carboxyl groups of the productshereinabove described and hydroxy groups of the alcohols. If desired,the free carboxyl groups may be converted to acyl halides and thenreacted with the alcohols. The reaction may be accelerated, by the useof the usual condensing agents such as sulphuric acid, chlorsulphonicacid, and 'the like. Such reactions may also be carried out between theproducts of the present invention, as described irrthe various examples,listed hereinabove, and the products described in the application ofBenjamin B. Harris, Serial. N0, 243,099, filed November 30', 1938.Particularly valuable products result from the interaction between theproducts of the presentinvention, as described in the various exampleslisted hereinabove, and such compounds as the mono-tartaric acid esterof glycerin, the mono-citric acid esters of ethylene glycol anddiethylene glycol, the ester resulting from one mol of glycerin and twomols of tartaric acid, and, in general, the water-soluble andwater-dispersible esters of aliphatic polyhydroxy substances withpolycarboxylic and hydroxypolycarboxylic acids. Such esters aredisclosed as intermediate products in the preparation of thecompoundsdisclosed in the aforementioned application of Benjamin R. Harris.

The hydroxy polycarboxylic acid anhydrides whose acetic acid esters andsimilar derivatives are reacted with alcohols, amides, amines, and thelike, to produce products for use in accordance with the presentinvention may be selected from a large group including, for example,citric acid, tartaric acid, malic acid, hydroxy methylsuccinic acid,trihydroxyglutaric acid, muclc acid, saccharic acid, and the monoandpoly-hydroxy derivatives of adiplc acid, pimelic acid, suberlc acid,azelaic acid, sebacic acid, and the like. It

is preferred to employ the acetic acid esters or like derivative of theanhydrides of those hydroxy polycarboxylic acids which are water-solubleand of aliphatic character. These acids may contain other substituentssuch as N'Ha, F, Cl, Br, I, etc. citric and tartaric acids,

In place of the acetic acid ester derivatives of the anhydrides of thehydroxy polycarboxyiic acids, I may employ any carboxylic acidderivative, preferably water-soluble and of aliphatic or fatty characterand particularly containing not more than six carbon atoms although theinvention is not so limited. Examples of such derivatives are those frompropionic acid, butyric acid, valeric acid, maleic acid, succinic acid,and the like. Of particular utility, however, are the acetic acid esterderivatives.

The alcohols which are reacted with the acetic acid esters of thehydroxy polycarboxylic acid anhydrides may be selected from a largegroup example, 2-ethyl hexanol-l, 2-n butyl octanol-l,

Z-butyl tetra-decanol-l, and, in general, the higher molecular weightsaturated and unsaturated aliphatic straight chain and branched chainalcohols. Preferably, the alcohols which are utilized are thosecorresponding to the fatty acidsoccurring in triglyceride oils and fatsof vegetable or animal origin, natural or hydrogen- Of' particularimportance are tended to include alcohols which may or may not containother groups such as carboxylic, car- .bonyl, halogen, or otherradicals.

The alcohols obtainable by substituting alkyl or 'acyl radicals,preferably of high molecular weight, in place of the hydrogen of one ormore hydroxy groups of polyhydroxy substances or polyhydric alcohols, itbeing understood that at least one hydroxy group attached to the nucleusof the polyhydroxy substance or polyhydric alco-- hol remains, are alsowithin the scope of the alcohols from which compounds useful for thepurposes of the present invention may be produced. As examples of suchalcohols may be mentioned partially esterified or partially etherifiedmono-, di-, and poly-saccharides, and sugar alcohols such as monolauricacid ester of sucrose, monostearic acid ester of dextrose, mono-paimiticacid ester of sorbitol, monolauryl ether of pentaerythritol, monolauricacid ester of pentaerythritol, and the like; the monoglycerides anddi-glycerides, preferably of the higher fatty acids, including, forexample, monoacetin, dibutyrin, monolaurin, monomyristin, monostearin,mono-olein, distearin, diolein, dicaproin, mono-lauryl ether ofglyceroLmono-oleyl ether of glycerol, mono-cetyl ether of glycerol,di-cetyl ether of glycerol, monoa.

stearyl ether of glycerol, mono-stearic acid ester of diethylene glycol,monolauric acid ester'of ethylene glycol, monolauric acid ester oftriethanolamine, monostearic acid ester of tripropanolamine, and thelike. The aliphatic polyhydroxy substance which is partially esterifiedor etherified to provide one of the reacting constituents herein may beselected from a large class and includes, among those mentioned,glycerol; glycois such as ethylene glycol, propylene glycol,trimethylene glycol, butylene glycol and the like;

polyglycols such as diethylene glycol; pentaerythritol; quercitol;dihydroxy acetone; triethanolamine; tripropanolamine; polyglycerols suchas diglycerol, 'triglycerol, tetraglycerol and the like ated, such ascorn oil, cottonseed ofl, sesame oil,

coconut oil, palm kernel oil, sunflower seed'oil, lard, tallow, soyabean oil and the like, those alcohols containing from 12 to 18 carbonatoms being preferred. Other alcohols which may be employed are thecycloaliphatic or ali-cyclic alcohols such as the sterols, as, forexample, cholesterol, iso-cholesterol, phytosterol, sitosterol,hydroaromatic alcohols such as abietol, and such unsaturated alcohols aslinalool, citronellol, geraniol and the like and hydrogenated productsof the foregoing. Also included within the class of alcohols which maybe employed are such compounds as the hydroxy and alpha-hydroxy higheraliphatic and fatty acids as, for example, ricinoleic acid,alpha-hydroxy stearic acid, alphahydroxy lauric acid, di-hydroxy stearicacid, l-

hydroxy-stearic acid, alpha-hydroxy paimitic acid, and the like, as wellas esters of hydroxyfatty acids, such as ethyl ricinoleate, castor oil,butyl alpha-hydroxystearate, cetyl hydroxystearate, and the like. Stillother alcohol molecules are the carboxylic acid amides of alkylolaminessuch as lauric acid amide of mono-ethanolamine, oleic acid amide ofmono-propanolamine, and the like.

The term alcohols," as employed herein, is in-' including mixturesthereof; carbohydrates and sugars including mono, diand polysaccharides,such as dextrose, sucrose, xylose, arabinose, ga-' lactose, fructose,maltose, mannose, dextrin, starch, and the like; the natural andsynthetic, simple and complex gucosides; sugar alcohols such asarabitol, mannitol, sorbitol anddulcltol;

and polyhydroxy-carboxylic acids such as tartaric acid, mucic acid,saccharic acid, gluconic acid, glucuronic acid, gulonic acid, mannonicacid, trihydroxyglutaric acid, glyceric acid, carboxyllc oxidationproducts of polyglycerols, others of similar character, and hydroxyethyland hydroxypropyl ether derivatives of the above, as, for example:

H-OCHa-CH2OH H:OCH2CH20H cmo-cmcmon n-o-cm-cflion H-O-CHr-CHaOHn-o-om-omon H-Q-CHr-CHzOH 1 m-o-om-cmon (For convenience, all hydroxylgroups are written facing one way). In general, this type of alcohol maybe represented by the formula wherein R is a radical selected from thegroup consisting of alkyl, cyclo-alkyl, aryl, aralkyl', and

acyl, and substitution products thereof, X is the residue of thealiphatic polyhydroxy substance, and '0 and w are small whole numbers.

It is, of course, obvious that the alcohols from which the compoundsdisclosed herein may be produced may be prepared in accordance with anydesired method. For example, many of these alcohols may be prepared bythe so-called Bouveault and Blanc method or, alternatively, by thereduction or catalytic reduction with hydrogen of natural orhydrogenated animal or vegetable fats and oils, or mixtures thereof, inaccordance with well, known practices. Again the alcohols may be derivedfrom synthetic processes such as by the oxidation of hydrocarbons or maybe. prepared by saponification of waxes and the like. Alternatively,they may be prepared -by reduction of aldehydes or by the Grignardreaction.

It is likewise apparent that mixtures of the foregoing or other alcoholsor their derivatives may be utilized in the preparation of the compoundsas, for example, the mixture of alcohols resultingfrom the hydrogenationof coconut oil or the free fatty acids of coconut oil. Lauryl alcoholcomprises about 45% of the total alcohol mixture, the remaining alcoholsrunning from C6 to C18. Again, mixtures of alcohols such as are presentin the so-called sperm oil alcohols, as well as those present inwool-fat, may efficavciously be utilized. Indeed, these higher molecularweight alcohols are generally offered on the market in the form ofmixtures of different alcohols. If desired for any specific purpose,special fractions which predominate in a certain particular highermolecular weight alcohol may be utilized or, if so desired, the productsmay be prepared from a single, substantially pure alcohol.

.The reaction products may be used as such 'or they may be neutralized,in whole or in part, with suitable anti-acid materials. In thisconnection, considerable latitude and modification may be exercised. Ingeneral, inorganic as well as organic anti-acid agents may be employed.Examples of such agents which may be used satisfactorily arebicarbonates of the alkali metals, potassium hydroxide, potassiumcarbonate, metallic sodium, sodium hydroxide, sodium oxide, sodiumcarbonate, ammonium hydroxide, ammonia gas, calcium and magnesiumoxides, hydroxides, and salts, potassium. stearate, sodium stearate, andthe like.

It will be understood that bythe term cation, as used throughout thespecification and claims, is meant hydrogen and such other elements asare mentioned herein, and, in general,

atoms or radicals which are regarded as hearing a positive charge orcapable of replacing acidic hydrogen. The reaction products may beneutralized to methyl orange, litmus or phenolphthalein or to anydesired hydrogen ion concentration. As a general rule, if the salts ofthe reaction products are employed, it is preferred to use the sodium,potassium, ammonium, or

other soluble salts.

It will be seen, from a consideration of the numerous examples listedhereinabove, that the chemical compounds fall into two distinctcateglycerol, and the like.

especially important phase of the present invention.

It will be understood that the compounds need not be utilized in thepure state. Indeed, in most instances it will be found to be moreconvenient and commercially desirable to employ them in the form oftheir"reaction' mixtures with or without the addition of diluents. Itwill also be understood that mixtures of any one or more of the reactingconstituents may be employed in producing the products hereof and thisis particularly the case where commercial supplies of the chemicals areutilized; and, in addition, any of the esters of the hydroxy pnlcarboxylic acid anhydrides listed above may be, reacted with any of thealcohols descrim The following examples are illustrative of my! iouscompositions falling within the scope of the. invention. It will beunderstood that these are given only by way of example and are not tobe. construed as limitative of the invention in any manner. Thus, forexample, different reaction products or mixtures of any two or more ofthem may be employed, different essential oils and different vitamin Aand D concentrates of varying potency may be utilized, the proportionsof materials may vary, and other changes may be made without departingfrom the spirit and teachings of the invention herein.

Example I To 10 parts by weight of an irradiated ergosterol having1,000,000 U. S. P. units of of vitamin D per gram there is added 300parts by weight of a product comprising essentially the monooleyl esterof the acetic acid ester of citric acid. The resulting product isreadily dispersible in aqueous media to form a uniform, homogeneousproduct.

Example II To 20 parts by weight of a sample of halibut liver oilfortified with irradiated ergosterol, so as to. provide a, producthaving 45,000 U. S. P. units of vitamin A per gram and 300,000 units ofvitamin D per gram, there are added parts by weight of a reactionproduct of mono-oleinwith the acetic acid ester of citric acidanhydride. The resulting product is readily dispersible in aqueous mediasuch as milk to provide a uniform, homoparticularly satisfactory andtheir use constitutes an eneous emulsion containing from 850 to 900 Theessential oils may also be selected from a nits of vitamin A per liter.large group and may be of natural or synthetic Example IV character.They may be distributed or sold in admixture with the chemical compoundor reac- 1710!! Products described herein so that the composition may bedispersed in aqueous media or the like. Alternatively, the aqueousdispersions of such compositions may initially be prepared and sold ormerchandised in such form.

The proportions of the chemical compounds utilized herein are subject torelatively wide variation. The selection of proportions depends upwd meta? tartaric acid anhydnde' The re on the potency of the particularchemical comi? product is readily dispersible m m pound utilized, the.nature 01 the composition j sought to be prepared, and the character ofthe A composition is made up containing 50 parts by weight of irradiatedergosterol having a potency of 2,000,000 U. S. P, units of vitamin D-':per gram, 18 parts by weight'oi a concentrate of Vitamins B and Gprepared from brewer's yeast,

parts by weight of calcium gluconat'e, and 325 parts by weight of aproduct comprising predorninately the mono-oleyl ester of the di-aceticExample V I results desired. In general, depending upon these A isPrepared containing 100 Parts factors, the proportions may range from afraci Weight of lemon 011 and 10 Parts by weight tion of 1% to severalpercent. Those skilled in lot the reaction product of mono-oleinand thedithe art will readily be able select proper acetic acid ester oftartaric acid anhydride; The 20 p t in t light of our teachings herein,Tesulting composition is readily 0r 4 What we claim a 'new and de ireprotect dispersed 1180115 media- Letters Patent of the United States is:i Example VI 1 "1; A composition which is adapted to disperse Acomposition is prepared containing 100 parts in aqueous media comprisinga in ocuous base iby weight of orange oil and 8 parts by weight ofingredient and a proportion of a water-soluble the reaction product ofdi-olein and the acetic water-'dispersible Chemical p d c p isiaeidester of citrld acid anhydride, h compoing a reaction product of ananhydride of a. car- 'sltion dispersed wellin aqueousmedia. bcxylic a dst r "vi a y x p y arbcxylic instances where the chemical compounds orres e of P l rs a d p rtia es ers 01 allaction products are employed inedible prepara= phallic D Y Y Y substancestlons or are t be takenlntemally, only those 2. An edible composition which is adapted to willbe utilizedwhich are d'efinitely innocuous; d p in aqueousmediapomprlsing an edible Those skilled 1 t t will be able readily toleaginous material and a proportion of a waterselect compounds orreaction product w l are soluble to water-dispersible chemical compoundsuitable for edible purposes inthe light of my eg containing at leastone carboxyl group in its tmtidnherem; A V i molecule and comprising area i n product of a The source 01 the vitamin concentrates or the lowedmolecular Weight aliphatic a b xylic acid It will be understood, orcourse, that, inthose acid and c mmbcr selected from the oup con-.

like is, of course, immaterial. Thus, for example, ester an aliphatic yy p y oxyl c: acid 'there may be employed fish liver oils such as codanhydride and a member selected from he o p liver oil, salmon liver oil,halibut liver oil, or other s sting of higher' 111018611181 Weight pa tal oils, or concentrates prepared therefrom by exethers and Partialesters of aliphatic P y ydr y traction, saponifi'cation, moleculardistillation, .Sllbstancesaha other' kfiown treatmentis'tepsf'Products'such' A composition co a n a'mcmber select ascarotene, ultra-violet ray irradiated ergosterol 4 ed m the group con in f p ovl amins and or derivatives of ergosterol, cathode-ray andoil-soluble vitamin concentrates and a proporelectrodeless dischargeactivated products, and t1011. Of an innocuous Water-Soluble towater-dis- -the like mayalso beutilized, W, V d d m persible chemicalcompound comprising a reacwm qm the gg amples herelmbove, there has tionproduct or an anhydride or a carboxylic been disclosed thememployment ofvitamin cond 5 O y o y polycarboxylic acid and centrates having certainspecified potencies, it is a member e cted from the groun o lsting ofobvious ,that o the invention 9 circum- Partial ethers and partialesters of aliphatic polyicrib'edirxThusfi foriiexeznpliaviwfl gfinn l xysubstances.

. trates'*n'ialr ce'"utilized-12oattainingas -higkpag. ..-;;4. Acomposition containing an ouisomm v15 2,000,000=ormore units ofvitamiirskpengram fi, V H V diluted in oi1,to.which,10%, .ormorejori'e'ss', of sisting or vitamins A and D and mixtures ther'eof', achemical compound or reaction product of the nd a proportion of awater-soluble to water-dis= type:heroia desorrhoos s 1?" a-Similarly} asindicated, mixtures of vitamins A and D of tion product of an anhydrideof an acetic acid ,tamin concentrate selected from the group con- Vpersible chemical compound comprising areacei'iTdlfigly'"i'iigl'fpotencyTpreferablydissolvedinGO-" f nliphtichydr yp ly ar vl id an oil, may be mixed with b ut; 10% to about anda member selected from the group consisting 20% Y of such chemicalcompounds or reaction O higher molecular weight f y acid partialesproducts and distributed in that form with dirs f lip ati pc y y ysubstances s lec ed rections for dilution with water, milk or other frome roup consisting f l rol, lyc laqueousmaterlag tg providelopprgperdosage, 5 polyglycerols, polyglycols, sugars, sugar alcohols,

As indicated in the above examples, the'vita and hydroxycarboxylicacids." min preparations may be supplemented by the 5. A compositioncontaining a vitamin D conaddition thereto of sources or concentrates ofcentrate and a proportion of a water-soluble to water-soluble vitaminssuch as vitamins B and water-dispersible chemical compound corre- G, andalso sources of assimilable calcium may be sponding to that resultingfrom the interaction added to p e o positions having the necof an aceticacid ester of an aliphatic hydroxy essary factors to supply certaindietary defipolycarboxyllc acid anhydride with a higher mociencies.These and other variations are within iecular weight fatty acidmonoglyceride, said the scope of the invention as pointed out in thecomposition having a potency of at least 100,000

appended claims. U. S. P. units of vitamin D per gram.

uld to pasty consistency corresponding to that resulting from theinteraction of an acetic acid ester of an aliphatic hydroxypoiycarboxylic acid anhydride with a higher molecular weight unsaturated fatty acid partial ester of an aliphatic polyhydroxysubstance, said composition being distributed in an aqueous medium andcontaining at least 100,000 U. 8.? units of vitamin 1) per gram. a

7. A composition containing an irradiated 'pro-' vitamin D material, atleast one water-soluble vitamin, a source of assimilable calcium, and aproportion of an innocuous water-soluble to wa ter-dispersible chemicalcompound comprising a reaction product of an anhydride 01' a carboxylicacid ester of a hydroxy polycarboxylic acid and a member selected fromthe group consisting of partial ethers and partial ester of aliphaticpolyhydroxy substances.'

8. A composition containing an essential oil and a proportion of awater-soluble to. waterdispersible chemical compound comprising areaction product of an anhydride of a carboxylic' acid ester of ahydroxy polycarboxylic acid and a member selected from the groupconsisting of partial ethers and partial esters of aliphatic polyhydroxysubstances.

9. A composition containing a substantial proportion of an essential oiland a major proportion of a water-soluble vto water-dispersible chemicalcompound of normally liquid to pasty consistency corresponding to thatresulting from the interaction of an acetic acid ester of an allphatichydroxy polycarboxylic acid anhydride with a higher molecular weightunsaturated fatty acid partial ester of an aliphatic polyhydroxysubstance, said composition being dispersible in aqueous media. 1

"10. A composition containing amember selected from the group consistingof provitamins and oil-soluble vitamin concentrates and a proportion ofan innocuous water-soluble to water-dispersi- .ble chemical,co,mpound.having ,the...general for-- mulaococn;

t icocni wherein Z is the radical of a member selected from the groupconsisting of partial ethers and -mern ber selected partial esters ofaliphatic polyhydroxy substances, and X is a cation.

12. A composition containing a vitamin D concentrate and a proportion ofan innocuous watersoluble to water-dispersible chemical compoundcomprising an ester of an alcohol containing at least four carbon atomswith the acetic acid ester of citric acid, and salts thereof.

13. A composition containing a member selected from the group consistingof provitamins and oil-soluble vitamin concentrates and a proportion ofan ester of oleic acid in accordance with the general formula .whereln Xis a cation.

14. A composition which is adapted to disperse in aqueous mediacomprising an innocuous base ingredient and a proportionof awatersoluble to water-dispersible chemical compound of normally liquidto pasty consistency corresponding to that resulting from theinteraction of an acetic acid ester of an aliphatic hydroxypolycarboxylic acid anhydride with a. higher molecular weightunsaturated fatty acid partial ester of an aliphatic polyhydroxysubstance.

15. An edible composition which is adapted to disperse in aqueous mediacomprising an edible oleaginous material and a proportion of aninnocuous water-soluble to water-dispersible chemical compoundcomprising an ester of a lower molecular weight carboxylic acid ester ofa hydroxy polycarboxylic acid with a compound selected from the groupconsisting of partial one carboxyl group in its molecule and comprisinga reaction product of a lower molecular weight aliphatic carboxylic acidester of an allphatic hydroxy polycarboxylic acid anhydride and amemberselected from the group consisting of higher molecular weightpartial ethers and partial esters of aliphatic polyhydroxy substances. v

18. A composition containing an oil-soluble vitamin concentrate,oleaginous material, and a proportion of a water-soluble towater-dispersible chemical compound of normally liquid to pastyconsistency corresponding to that'resulting from the interaction of anacetic acid ester of an aliphatic hydroxy polycarboxylic acid anhydridewith a higher molecular weight unsaturated Iaty acid partial ester of analiphatic polyhydroxy substance.

19. A composition containing aqueous material, oleaginous material, avitamin concentrate, and a proportion of a water-soluble towater-dispersibie chemical compound of normally liquid to pastyconsistency and comprising an ester of a lower molecular weightcarboxylic acid ester of .a hydroxy polycarboxylic acid with a compoundselected from the group consisting oi. partial ethers and partial estersoi. glycerol.

20. A composition containing vitamin D concentrate and a proportion of awater-soluble to water-dispersible chemical" compound comprising aninnocuous ester of an alcohol containing at least four carbon atoms withthe acetic acid ester of citric acid, and salts thereof.

21. A composition which is adapted to disperse in aqueous mediacomprising an innocuous base ingredient and a proportion of awater-soluble to water-dispersible chemical compound compris ing anester of a lower molecular weight carboxylic acid ester of a hydroxypolycarboxylic acid with an alcohol containing at least four carbonatoms.

22. A composition containing a member selected from the group consistingprovitamins and oil-soluble vitamin concentratesand a proportion of aninnocuous water-soluble to waterdispersible chemical compound comprisingan ester of a lower molecular weight carboxylic acid ester of a hydroxypolycarboxylic acid-with an alcohol containing at least four carbonatoms.

23i A composition containing an essential oil and a proportion of awater-soluble to waterdispersible chemical compound comprising an esterofa lower molecular weight carboxylic acid ester of a hydroxypolycarboxylic acid with an alcohol containing at least four carbonatoms.

FRANK J; CAI-1N. BENJAMIN R. HARRIS.

